TWI826890B - Nozzle cleaning method, substrate processing method, semiconductor device manufacturing method, substrate processing device and program - Google Patents

Abstract

[Issue] The film thickness variation during the film formation process can be reduced by effectively removing residual elements after cleaning. [Solution] After the substrate is processed and unloaded in a reaction tube having a plurality of nozzles, there are: (a) a process of supplying a cleaning gas to at least one of the plurality of nozzles, (b) a process of (a) The process of supplying gas containing hydrogen and oxygen to at least one nozzle, and (c) the process of loading the next substrate into the reaction tube after the process of (b).

Description

Nozzle cleaning method, substrate processing method, semiconductor device manufacturing method, substrate processing device and program

The present disclosure relates to a nozzle cleaning method, a substrate processing method, a semiconductor device manufacturing method, a substrate processing device and a program.

As one of the manufacturing processes of semiconductor devices, there is a case where a substrate is processed in a processing container (see, for example, Patent Document 1). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2016-157871

[Problem to be solved by the invention]

In the use of semiconductor manufacturing equipment, by repeating the film formation process, the accumulated film in the reaction chamber may peel off due to stress, which may cause problems such as particles. Therefore, when a certain degree of film accumulates, cleaning may be performed in order to remove the film. In recent years, as a cleaning means, gas cleaning in which a reaction gas is used to remove a built-up film has been used.

As the cleaning gas, there is a method of using a gas containing fluorine (F) such as _F2 or _NF3 . In this method, after cleaning is completed, elements such as fluorine contained in the cleaning gas may remain, which may hinder the film formation process. In this case, problems such as film thickness variation may occur during the film forming process before and after cleaning. As a countermeasure to this problem, there are means for removing residual elements by using NH ₃ gas treatment, or means for sealing residual elements by overlapping accumulation films and coating.

The present disclosure provides means for reducing film thickness variation during film formation by effectively removing residual elements after cleaning. [Means used to solve problems]

If a technology is provided in one aspect of this disclosure, the technology is After the substrate is processed in a reaction tube with multiple nozzles and moved out, it has: (a) A process of supplying cleaning gas to at least one of the plurality of nozzles mentioned above, (b) A process of supplying gas containing hydrogen and oxygen to at least one of the nozzles after performing the process of (a) above, (c) After the process in (b) above, the process of moving the next substrate into the above reaction tube. [Effects of the invention]

According to this disclosure, residual elements after cleaning can be effectively removed, thereby reducing film thickness variation during the film formation process.

＜Aspect of this disclosure＞

Hereinafter, one aspect of the present disclosure will be described using drawings as appropriate. In addition, the drawings used in the following description are all schematic, and the dimensional relationships and ratios of each element in the drawings may not necessarily match those in reality. Furthermore, even among a plurality of drawings, the relationship between the dimensions of each element, the ratio of each element, etc. are not necessarily consistent.

In this specification, the term "wafer" may mean the wafer itself or a laminate of the wafer and a specific layer or film formed on its surface. In this specification, when the phrase "surface of wafer" is used, it may mean the surface of the wafer itself or the surface of a specific layer or film formed on the wafer. In this specification, when it is described as "forming a specific layer on the wafer", it may mean that the specific layer is formed directly on the surface of the wafer itself, or it may mean that the specific layer is formed on a layer formed on the wafer. The formation of a specific layer. In this specification, the term "substrate" is also synonymous with the term "wafer". In addition, the wafer or substrate on which the specific layer or film is formed is called a "semiconductor device."

(1) Structure of substrate processing equipment As shown in FIG. 1 , the treatment furnace 202 includes a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 has a cylindrical shape and is vertically installed by being supported on a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas using heat.

Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a branch tube 209 is arranged concentrically with the reaction tube 203. The branch pipe 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an upper end and a lower end open. The upper end of the branch pipe 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. Between the branch pipe 209 and the reaction tube 203, an O-ring 220a as a sealing member is provided. The reaction tube 203 and the heater 207 are also installed vertically. Mainly, the reaction tube 203 and the branch tube 209 constitute a processing vessel (reaction vessel). The processing chamber 201 is formed in the hollow part of the cylinder of the processing container. The processing chamber 201 is configured to accommodate the wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

In the processing chamber 201, nozzles 249a, 249b, and 249c are respectively provided as the first supply part, the second supply part, and the third supply part so as to penetrate the side wall of the branch pipe 209. The nozzles 249a, 249b, and 249c are also called a first nozzle, a second nozzle, and a third nozzle, respectively. The nozzles 249a, 249b, and 249c are each made of a heat-resistant material that is a non-metal material such as quartz or SiC. The nozzles 249a, 249b, and 249c are each configured as a common nozzle used for supplying a plurality of types of gases.

Gas supply pipes 232a, 232b, and 232c serving as the first pipe, the second pipe, and the third pipe are connected to the nozzles 249a, 249b, and 249c, respectively. The gas supply pipes 232a, 232b, and 232c are each configured as a common pipe used for supplying a plurality of types of gases. The gas supply pipes 232a, 232b, and 232c are respectively provided with mass flow controllers (MFC) 241a, 241b, and 241c as flow controllers (flow control units) and a valve body 243a as a switching valve in order from the upstream side of the gas flow. , 243b, 243c.

On the downstream side of the valve body 243a of the gas supply pipe 232a, the gas supply pipes 232d, 232e, 232f, 232g, and 232n are connected in this order. MFCs 241d, 241e, 241f, 241g, 241n and valve bodies 243d, 243e, 243f, 243g, 243n are respectively provided in the gas supply pipes 232d, 232e, 232f, 232g, and 232n in order from the upstream side of the gas flow. In addition, the second heater 207a is installed on the downstream side of the valve bodies 243d and 243e of the gas supply pipes 232d and 232e.

On the downstream side of the valve body 243b of the gas supply pipe 232b, the gas supply pipes 232h, 232i, 232j, and 232o are connected in this order. MFCs 241h, 241i, 241j, 241o and valve bodies 243h, 243i, 243j, 243o are provided in the gas supply pipes 232h, 232i, 232j, and 232o in order from the upstream side of the gas flow. In addition, the second heater 207b is installed on the downstream side of the valve bodies 243b and 243h of the gas supply pipes 232b and 232h.

On the downstream side of the valve body 243c of the gas supply pipe 232c, the gas supply pipes 232k, 232l, 232m, and 232p are connected in this order. MFCs 241k, 241l, 241m, 241p and valve bodies 243k, 243l, 243m, 243p are provided in the gas supply pipes 232k, 232l, 232m, and 232p in order from the upstream side of the gas flow. In addition, the second heater 207c is installed on the downstream side of the valve bodies 243c and 243k of the gas supply pipes 232c and 232k.

The gas supply pipes 232a to 232p are made of metal material. In addition, the material of the branch pipe 209 and the materials of the sealing cover 219, the rotating shaft 255, and the exhaust pipe 231 described later may be the same as the gas supply pipes 232a to 232m.

As shown in FIG. 2 , the nozzles 249 a , 249 b , and 249 c are respectively arranged in an annular space when viewed from above between the inner wall of the reaction tube 203 and the wafer 200 . The lower part stands upright along the upper part toward the arrangement direction of the wafers 200 . That is, the nozzles 249 a , 249 b , and 249 c are disposed along the wafer array area in an area horizontally surrounding the wafer array area on the side of the wafer array 200 . Gas supply holes 250a, 250b, and 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a, 249b, and 249c. The gas supply holes 250a, 250b, and 250c each open along the center of the wafer 200 in a plan view, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a, 250b, and 250c are provided from the lower part to the upper part of the reaction tube 203.

The raw material gas system is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC 241a, the valve body 243a, and the nozzle 249a. The raw material gas system is a gas obtained by vaporizing a raw material in a gaseous state, such as a raw material that is in a liquid state at normal temperature and pressure, or a raw material that is in a gaseous state at normal temperature and normal pressure.

The first reaction gas system is supplied into the processing chamber 201 from the gas supply pipes 232b, 232d, and 232k via the MFCs 241b, 241d, and 241k, the valve bodies 243b, 243d, and 243k, and the nozzles 249b, 249a, and 249c, respectively.

The second reaction gas system is supplied into the processing chamber 201 from the gas supply pipes 232c, 232e, and 232h via the MFCs 241c, 241e, and 241h, the valve bodies 243c, 243e, and 243h, and the nozzles 249c, 249a, and 249b, respectively. In addition, the second reaction gas may be a gas of different molecules from the first reaction gas, or may be a gas of the same molecule. In the following description, an example in which a gas having molecules different from that of the first reaction gas is used in the second reactant gas system will be described.

The cleaning gas system is supplied to the processing chamber from the gas supply pipes 232f, 232i, and 232l via the MFCs 241f, 241i, and 241l, the valve bodies 243f, 243i, and 243l, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c, respectively. Within 201.

The additive gas system is supplied into the processing chamber 201 from the gas supply pipes 232g, 232j, and 232m respectively via the MFCs 241g, 241j, and 241m, the valve body 243g, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a, 249b, and 249c.

As the inert gas, for example, nitrogen (N ₂ ) gas is supplied from the gas supply pipes 232n, 232o, and 232p via the MFCs 241n, 241o, and 241p, the valve bodies 243n, 243o, and 243p, the gas supply pipes 232a, 232b, and 232c, and the nozzles 249a and 249b, respectively. , 249c and is supplied into the processing chamber 201. The N ₂ gas system functions as a purge gas, carrier gas, diluent gas, etc.

The raw material gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, the valve body 243a, and the nozzle 249a. Mainly, the first reaction gas supply system is composed of gas supply pipes 232b, 232d, 232k, MFCs 241b, 241d, 241k, valve bodies 243a, 243b, 243c, and nozzles 249a, 249b, 249c. Mainly, the second reaction gas supply is composed of gas supply pipes 232c, 232e, 232h, MFC 241c, 241e, 241h, valve bodies 243c, 243e, 243h, gas supply pipes 232c, 232a, 232b, and valve bodies 249c, 249a, 249b. system. In addition, the first reaction gas supply system and the second reaction gas supply system may be collectively referred to as a reaction gas supply system. Mainly, the cleaning gas supply system is composed of gas supply pipes 232f, 232i, 232l, MFC241f, 241i, 241l, and valve bodies 243f, 243i, and 243l. The cleaning gas supply system may include gas supply pipes 232a, 232b, and 232c and nozzles 249a, 249b, and 249c. Mainly, the additional gas supply system is composed of gas supply pipes 232g, 232j, 232m, MFCs 241g, 241j, 241m, valve bodies 243g, 243j, 243m, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c. Mainly, the inert gas supply system is composed of gas supply pipes 232n, 232o, 232p, MFC 241n, 241o, 241p, valve body 243n, 243o, 243p, gas supply pipes 232a, 232b, 232c, and nozzles 249a, 249b, 249c.

Any or all of the above various supply systems may be configured as an integrated supply system 248 composed of integrated valve bodies 243a to 243p, MFCs 241a to 241p, or the like. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232p, and is configured to control the operation of supplying various gases into the gas supply pipes 232a to 232p by the controller 121 described later, that is, one of the valve bodies 243a to 243p. Switching action or flow adjustment action caused by MFC241a~241p, etc. The integrated supply system 248 is configured as an integrated unit or a divided type. The gas supply pipes 232a to 232p and the like can be attached and detached in units of integrated units. The integrated supply system 248 is configured to be able to be installed in units of integrated units. Repairs, replacements, additions, etc.

An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. The exhaust port 231a may be provided from the lower part along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement area. The exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is connected to a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). A vacuum valve 246 serving as a vacuum exhaust device is connected. The APC valve 244 is configured to perform vacuum evacuation and vacuum evacuation stop in the processing chamber 201 by opening and closing the valve body while the vacuum pump 246 is actuated. Next, the pressure in the processing chamber 201 is adjusted by adjusting the valve opening according to the pressure information detected by the pressure sensor 245 . Mainly, the exhaust pipe 231, the APC valve 244, and the pressure sensor 245 constitute an exhaust system. It is also possible to include the vacuum pump 246 in the exhaust system.

Below the branch pipe 209, a sealing cover 219 is provided as a furnace mouth cover capable of airtightly closing the opening at the lower end of the branch pipe 209. The sealing cover 219 is made of a metal material such as SUS, and is formed into a disk shape. On the upper surface of the sealing cover 219, an O-ring 220b as a sealing member that comes into contact with the lower end of the branch pipe 209 is provided. Below the sealing cover 219, a rotation mechanism 267 for rotating the wafer boat 217 described below is provided. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217 . The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217 . The sealing cover 219 is configured to be raised and lowered in the vertical direction by the wafer boat lifter 115 which is a lifting mechanism provided outside the reaction tube 203 . The wafer boat lifter 115 is configured as a transport device (transport mechanism) that can transport the wafer 200 into and out of the processing chamber 201 by lifting and lowering the sealing cover 219 . Below the branch pipe 209, a baffle 219s is provided as a furnace mouth cover that can hermetically seal the lower end opening of the branch pipe 209 when the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The baffle 219s is made of a metal material such as SUS, and is formed into a disk shape. On the upper surface of the baffle 219s, an O-ring 220c as a sealing member that comes into contact with the lower end of the branch pipe 209 is provided. The opening and closing operation (lifting, lowering, rotating, etc.) of the shutter 219s is controlled by the shutter switching mechanism 115s.

The wafer boat 217 as a substrate supporter is in a horizontal position and arranged in the vertical direction in a state in which the centers are consistent with each other, and supports a plurality of wafers 200 in multiple layers, for example, 25 to 200 wafers 200, which are arranged at intervals. way is constituted. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. Under the wafer boat 217, a heat shielding plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple layers.

In the reaction tube 203, a temperature sensor 263 as a temperature detector is provided. According to the temperature information detected by the temperature sensor 263, the power-on state of the heater 207 is adjusted so that the temperature of the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203 .

As shown in FIG. 3 , the controller 121 as a control unit (control means) is a computer equipped with a CPU (Central Processing Unit) 121 a, a RAM (Random Access Memory) 121 b, a storage device 121 c, and an I/O port 121 d. is constituted. The RAM 121b, the memory device 121c, and the I/O port 121d are configured to exchange data with the CPU 121a via the internal bus 121e. The controller 121 is connected to an input/output device 122 configured as, for example, a touch panel or the like.

The memory device 121c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. The memory device 121c stores in a readable manner a control program for controlling the operation of the substrate processing apparatus, a program recipe in which the order or conditions of film formation described later are recorded, or the order or conditions of cleaning described later are recorded. cleansing formula. The process recipe causes the controller 121 to execute each sequence in the film formation described below, and is combined to obtain a specific result, and functions as a program. The cleaning recipe causes the controller 121 to execute each sequence of cleaning described below and combines them to obtain a specific result, thereby functioning as a program. Hereinafter, the process formula, cleaning formula, control program, etc. are also collectively referred to as programs. Furthermore, the process formula or cleaning formula is also called a formula. When a statement called a program is used in this manual, it may include only the recipe alone, only the control program alone, or both. The RAM 121b is configured as a memory area (work area) that temporarily holds programs, data, etc. read by the CPU 121a.

The I/O port 121d is connected to the above-mentioned MFCs 241a to 241p, valve bodies 243a to 243p, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, second heaters 207a to 207c, Rotating mechanism 267, wafer boat lifter 115, baffle switch mechanism 115s, etc.

The CPU 121a is configured to read the control program from the memory device 121c and execute it, and to read the recipe from the memory device 121c in response to the input of an operation command from the input/output device 122. The CPU 121a is configured to control the flow rate adjustment operations of various gases caused by the MFCs 241a to 241p, the switching operations of the valve bodies 243a to 243p, the switching operations of the APC valve body 244, and the pressure sensor based on the content of the read recipe. 245, the pressure adjustment operation caused by the APC valve 244, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the temperature adjustment operation of the second heaters 207a~207c, and the rotation mechanism 267 The rotation and rotation speed adjustment action of the wafer boat 217 is caused by the wafer boat lifter 115, the lifting action of the wafer boat 217, the baffle 219s switching action caused by the baffle switch mechanism 115s, etc.

The controller 121 as the above-mentioned control unit is configured to perform (a) a process of supplying a cleaning gas to the at least one nozzle after processing the substrate (wafer 200) in the reaction tube 203 and unloading it, (b) processing the processed substrate (wafer 200 ). The process of supplying a gas containing hydrogen and oxygen to the at least one nozzle in the process (a), and (c) the process of loading the next substrate (wafer 200) into the reaction tube 203 after the process (b). In this way, the conveying mechanism, the cleaning gas supply system that supplies cleaning gas, and the reaction gas supply system that supplies gas containing hydrogen and oxygen are controlled.

The controller 121 can be configured by causing the above-mentioned program stored in the external memory device 123, that is, a program that causes the substrate processing apparatus to execute the following sequence by the computer, to be installed on the computer. (a) A step of supplying a cleaning gas to at least one of the plurality of nozzles 249a, 249b, and 249c after the substrate (wafer 200) has been processed and moved out of the reaction tube 203 having the plurality of nozzles 249a, 249b, and 249c. , (b) the step of supplying gas containing hydrogen and oxygen to the above-mentioned at least one nozzle after performing the process of the above-mentioned (a), and (c) After step (b), the next substrate (wafer 200) is loaded into the reaction tube 203. The external memory device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, and the like. The memory device 121c or the external memory device 123 is configured as a computer-readable recording medium. Hereinafter, these are collectively referred to as recording media. When the term "recording medium" is used in this specification, it may include only the memory device 121c alone, only the external memory device 123 alone, or both of them. In addition, the program may be provided to the computer without using the external memory device 123 and may use communication means such as a network or a dedicated line.

(2) Manufacturing method of semiconductor device The manufacturing method of the semiconductor device of the present disclosure using the above-mentioned substrate processing apparatus is After the substrate (wafer 200) is processed and unloaded in the reaction tube 203 having the plurality of nozzles 249a, 249b, and 249c, there is: (a) A process of supplying cleaning gas to at least one of the plurality of nozzles 249a, 249b, and 249c, (b) A process for supplying gas containing hydrogen and oxygen to at least one of the nozzles after performing the process in (a) above, and (c) After the process of (b) above, the process of loading the next substrate (wafer 200) into the reaction tube 203.

Here, in the above-mentioned manufacturing method, the number of "plural nozzles" in the above-mentioned substrate processing apparatus is three, but it is not particularly limited if there are two or more nozzles.

(2-1) Processing of the substrate (wafer 200) In the above manufacturing method, before the above process (a), the processing of the substrate (wafer 200) in the reaction tube 203 can be performed, for example, by performing a specific number of times ( n times (n is an integer greater than 1), this cycle is not performed simultaneously: Step 1 of supplying the raw material gas to the wafer 200 in the reaction tube 203 through the gas supply pipe 232a and the nozzle 249a. After supplying the raw material gas into the processing chamber 203, the reaction tube 203 is evacuated while supplying the purge gas via the gas supply pipe 232n and the nozzle 249a to remove the raw material gas remaining in the processing chamber. Step 3 of supplying the first reaction gas to the wafer 200 through the gas supply pipe 232b and the nozzle 249b, and supplying the second reaction gas through the gas supply pipe 232c and the nozzle 249c, and stopping the supply of the first reaction gas into the reaction tube 203 After the reaction gas and the second reaction gas are supplied, the inside of the reactor 203 is evacuated while supplying N ₂ gas as a purge gas through the gas supply pipes 232o and 232p and the nozzles 249b and 249c to remove residues in the processing chamber. In Step 4 of the first reactive gas and the second reactive gas, a film containing a specific element is formed on the wafer 200 as a film forming process. The exhaust treatment in steps 2 and 4 is performed from the exhaust port 231a through the exhaust pipe 231.

In addition, as the raw material gas, Si, which is a main element (specific element) constituting the film, and a halogenated silane-based gas of a halogen element are used. Halosilane refers to a silane having a halogen group. Halogen groups include chlorine group, fluorine group, bromine group, iodine group, etc. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like. As the halogen-based gas, for example, a raw material gas containing Si and Cl, that is, a chlorosilane-based gas, can be used. The chlorosilane-based gas volatilizes as a Si source. As the chlorosilane-based gas, for example, hexachloroethylsilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas can be used. The HCDS gas system contains an element (Si) that becomes solid independently under the above-mentioned processing conditions, that is, it is a gas that can deposit a film independently under the above-mentioned processing conditions.

As the first reaction gas, for example, hydrogen-containing (H) gas is used. As the H-containing gas, for example, hydrogen (H ₂ ) gas, including activated hydrogen-containing gas, can be used.

As the second reaction gas, for example, oxygen (O)-containing gas is used. As the O-containing gas, for example, oxygen (O ₂ ) gas, water (H ₂ O) gas, ozone (O ₃ ) gas, and gas containing activated oxygen can be used.

The above-mentioned film forming process is expressed as follows. In addition, "P/V" means the purification treatment and exhaust treatment in steps 2 and 4. (raw material gas → P/V → first reaction gas + second reaction gas → P/V)×n

(2-2) Cleaning process In the above-mentioned manufacturing method, the cleaning process of the above-mentioned step (a) can be implemented, for example, by supplying a cleaning gas from at least one of the nozzles 249a, 249b, and 249c into the reaction tube 203. . As the purge gas, for example, fluorine (F)-containing gas is used. As the fluorine-containing gas, for example, fluorine (F ₂ ) gas or nitrogen trifluoride (NF ₃ ) gas is used. In the following, an example using F ₂ gas as the purge gas will be described.

For example, when the source gas is supplied from the nozzle 249a, the cleaning gas may be supplied from the gas supply pipe 232f through the nozzle 249a. In this case, it is preferable not to supply the cleaning gas to the other nozzles 249b and 249c during the above-mentioned process (a). In this way, for example, when a quartz nozzle is used, etching caused by fluorine-containing gas can be suppressed through the nozzle that does not flow the cleaning gas, and as a result, the life of the nozzle can be extended.

On the other hand, during the above process (a), it is preferable to set the gas supply amount to the other nozzles 249b and 249c that do not supply the cleaning gas to substantially zero. In this way, the cleaning gas supplied from the nozzle 249a flows into the other nozzles 249b and 249c, so that the cleaning process of the nozzle to which the cleaning gas is not supplied can be performed.

In addition, the above process (a) can be implemented by supplying the cleaning gas from all the nozzles 249a, 249b, and 249c into the reaction tube 203. That is, by supplying the cleaning gas into the reaction tube 203 through each of the gas supply pipes 232f, 232i, 232l and the nozzles 249a, 249b, 249c, the uniformity of the cleaning process in the reaction tube 203 can be improved. In this case, the purge gas may be supplied to the reaction tube 203 from all the nozzles 249a, 249b, and 249c at the same time. In this way, by supplying the purge gas from all the nozzles 249a, 249b, and 249c at the same time, it is possible to suppress the intrusion of residual fluorine, reaction products (for example, HF) generated in the process (b) described below, and non-supply. Fluorine remains in the nozzle of the purge gas. At this time, if there is a period when the purge gas is supplied into the reaction tube 203 from all the nozzles 249a, 249b, and 249c, even if the supply start timing and the supply end timing of the purge gas in each nozzle do not coincide, However, from the viewpoint of preventing the intrusion of residual fluorine, HF, etc. into other nozzles, it is preferable that the supply end timing of the cleaning gas to each nozzle is consistent, and it is even more preferable that the start timing of supply of the cleaning gas be consistent.

In addition, it is preferable to supply the additive gas to the nozzle after performing the above process (a) among the plurality of nozzles. For example, when the cleaning gas is supplied from the nozzle 249a, the additional gas is supplied into the reaction tube 203 via the gas supply pipe 232g and the nozzle 249a. When the cleaning gas is supplied from the nozzle 249b, the additional gas is supplied into the reaction tube 203 via the gas supply pipe 232j and the nozzle 249b. When the cleaning gas is supplied from the nozzle 249c, the additional gas is supplied into the reaction tube 203 via the gas supply pipe 232m and the nozzle 249c.

In addition, as the additive gas, a nitrogen oxide-based gas containing nitrogen (N) and oxygen (O) is used. Although nitrogen oxide gas alone cannot exert a cleaning effect, it reacts with the cleaning gas to generate active species such as fluorine radicals and halogenated nitrosylated compounds, thereby enhancing the cleaning effect of the cleaning gas. . As the nitrogen oxide-based gas, for example, nitric oxide (NO) gas can be used. In this way, fluorine radicals (･F) can be generated by supplying, for example, a cleaning gas and an additive gas, thereby improving the efficiency of the cleaning process.

In addition, when supplying additional gas to the nozzle after performing the above step (a), it is preferable not to supply the cleaning gas and to supply the additional gas at the same time, but to alternately supply the cleaning gas. Accordingly, for example, direct reaction between the cleaning gas and the additive gas can be suppressed, and by suppressing the amount of generated fluorine radicals (･F), for example, etching of a quartz nozzle can be suppressed.

The processing of supplying the cleaning gas and the additive gas alternately in this manner can be expressed as follows (Process A) and (Process B). In addition, the mode of the cleaning process has several modes as will be described later. (Process A): (Purge gas→P/V→Added gas→P/V)×n (Process B): (Add gas→P/V→Purge gas→P/V)×n

＜Cleaning processing mode 1＞ (Process A) or (Process B) may be performed on one or more of the plurality of nozzles. That is, it may be configured to perform (process A) or (process B) on each of the plurality of nozzles. (Process A) or (Process B) can be performed on more than one nozzle, and the cleaning gas and the additional gas are mixed in a specific amount in the nozzle to clean the inside of the nozzle. Here, the specific amount refers to, for example, the amount of the cleaning gas adsorbed and remaining in the nozzle and the amount of the additional gas that is supplied later and reacts with it.

＜Cleaning processing mode 2＞ Furthermore, it is also possible to perform (Process A) or (Process B) simultaneously on all the nozzles. By performing this operation on all nozzles at the same time, the cleaning speed of all nozzles or their surroundings can be made consistent.

＜Cleaning processing mode 3＞ Furthermore, the configuration may be such that (Process A) is performed on one nozzle and (Process B) is performed on other nozzles. Specifically, the structure is such that (process A) is performed in the nozzle 249b and (process B) is performed in the nozzle 249c. With this configuration, the cleaning gas and the additive gas are simultaneously supplied into the reaction tube 203 . By supplying the cleaning gas and the additive gas at the same time, the efficiency of the cleaning process in the reaction tube 203 can be improved. Furthermore, by sequentially changing the supply positions of the cleaning gas and the additive gas, it is possible to suppress deviations in cleaning within the plurality of nozzles or within the reaction tube 203, and the inside of the nozzles and the inside of the reaction tube 203 can be cleaned uniformly.

In addition, at this time, the inert gas may be continuously supplied to the nozzle 249a (process C). By continuously supplying the inert gas through the nozzle 249a, a sudden reaction between the gas supplied from the nozzle 249b and the gas supplied from the nozzle 249c on the nozzle side in the reaction tube 203 can be suppressed. Furthermore, the inert gas supplied from the nozzle 249a can function as a guide for the gas supplied from the nozzle 249b and the nozzle 249c, and can contribute to uniform cleaning in the reaction tube 203. In addition, (process A) or (process B) may be performed also in the nozzle 249a. Furthermore, the configuration may be to perform (Processing A) or (Processing B) and (Processing C) in order.

In addition, the cleaning process may be performed in combination with a plurality of the above-mentioned treatment patterns.

(2-3) Fluorine deactivation treatment In the above-mentioned manufacturing method, the fluorine deactivation treatment in the above-mentioned step (b) can be performed by supplying, for example, a cleaning gas to the nozzle that has been supplied to the reaction tube 203 in the above-mentioned step (a). gases containing hydrogen and oxygen. Here, the "gas containing hydrogen and oxygen" is preferably a mixed gas obtained by supplying hydrogen (H ₂ ) gas and oxygen (O ₂ ) gas from different gas supply pipes and mixing them at least in the nozzle, but even if Like water vapor (H ₂ O) or hydrogen peroxide (H ₂ O ₂ ), it may be a gas containing hydrogen (H) atoms and oxygen (O) atoms in one molecule. For example, a reaction equation representing a mechanism for removing fluorine (F ₂ ) or fluoride ions (F ^- ) remaining in the reaction tube using a mixed gas of H ₂ gas and O ₂ gas is considered to be as follows.

Furthermore, it is thought that water (H ₂ O) generated by the mixed gas of H ₂ gas and O ₂ gas causes the following reaction.

Here, by supplying the H ₂ gas as the first reaction gas and the O ₂ gas as the second reaction gas from separate gas supply pipes, and adjusting the flow rates according to the MFC of each, it is possible to adjust the flow rate to the reaction remaining in the nozzle. Fluorine removal treatment to remove the chemical state of fluorine in the pipe. For example, the flow rate ratio of each of the first reaction gas and the second reaction gas is changed according to the state of the fluorine remaining in the nozzle or the reaction tube. Furthermore, the flow rate ratio may be changed by adjusting the components to remove residual fluorine. Here, the component is a nozzle or reaction tube. For example, the process of removing residual fluorine in the nozzle and the process of removing residual fluorine in the reaction tube may have different flow rate ratios. Furthermore, the flow rate may be different for each process.

For example, when the cleaning gas is supplied from the nozzle 249a, the first reaction gas is supplied from the gas supply pipe 232d, and the second reaction gas is supplied from the gas supply pipe 232e, and is supplied as a mixed gas into the reaction tube 203 from the nozzle 249a. . When the cleaning gas is supplied from the nozzle 249b, the first reaction gas is supplied from the gas supply pipe 232b, the second reaction gas is supplied from the gas supply pipe 232h, and the mixed gas is supplied to the reaction tube 203 from the nozzle 249a. within. When the cleaning gas is supplied from the nozzle 249c, the first reaction gas is supplied from the gas supply pipe 232k, and the second reaction gas is supplied from the gas supply pipe 232c, and is supplied as a mixed gas into the reaction tube 203 from the nozzle 249a. .

Here, in the above process (a), when the purge gas is supplied into the reaction tube 203 from all the nozzles 249a, 249b, and 249c, the first gas is supplied from all the nozzles 249a, 249b, and 249c into the reaction tube 203. The mixed gas of the reaction gas and the second reaction gas can more reliably carry out the fluorine removal process in the reaction tube 203 . That is, when supplying to any nozzle, there is a possibility that residual fluorine or reaction products may invade into other nozzles (backflow into the nozzles), but by supplying from all nozzles, such backflow into the nozzles can be suppressed. .

In addition, in the process (b), the plurality of nozzles 249a, 249b, and 249c are heated by the heater 207 of the reaction tube 203 in such a manner that the gas containing hydrogen and oxygen is activated in the nozzles 249a, 249b, and 249c. Better. In this way, by heating and reacting H ₂ gas and O ₂ gas, in addition to water (H ₂ O), hydroxyl active species (･OH), oxygen active species (･O), and hydrogen active species can be produced (･O) General plural types of active species. Accordingly, even if the fluorine remaining in the reaction tube 203 exists in a plurality of chemical states, the fluorine remaining in the nozzles 249a, 249b, and 249c after the fluorine-containing gas is supplied can be deactivated by a plurality of active species, and Remove fluorine.

In addition, as described above, when the plurality of nozzles 249a, 249b, and 249c are heated by the heater 207 of the reaction tube 203, the main areas of the plurality of nozzles 249a, 249b, and 249c are heated substantially uniformly. temperature. In the main area of the plurality of nozzles 249a, 249b, and 249c, the first reaction gas and the second reaction gas react as described above, and the plurality of nozzles 249a, 249b, and 249c are heated. Specifically, at least one of the plurality of nozzles 249a, 249b, 249c and the heater 207 is disposed in the main area 249d of the plurality of nozzles 249a, 249b, and 249c so as to be disposed further inside the end of the heater 207. Here, the main area 249d of the nozzles 249a, 249b, and 249c refers to an area where various gases are supplied to the substrate (wafer 200), preferably the product substrate. In other words, the substrate (wafer 200) is supplied to the reaction tube 203. areas for various treatments. In addition, it is preferable that the area where the various gases are supplied to the substrate (wafer 200) includes a portion without gas supply holes 250a, 250b, and 250c provided in the nozzles 249a, 249b, and 294c to release the gases. Furthermore, it is preferable that the area where the gas supply holes 250a, 250b, and 250c are provided faces at least the heater 207. Furthermore, a substantially uniform temperature means that, for example, the temperature difference between the highest temperature point and the lowest temperature point in the area is within 3°C. In this way, by heating the main areas of the nozzles 249a, 249b, and 249c to a substantially uniform temperature, the fluorine deactivation treatment can be uniformly performed in the main areas of the nozzles 249a, 249b, and 249c. Furthermore, a plurality of types of active species generated in the main area 249d of the nozzles 249a, 249b, and 249c can be supplied to at least the processing area of the reaction tube 203 where the wafer 200 is placed. Accordingly, the processing area of the reaction tube 203 can be uniformly cleaned.

Here, the heater 207 is divided into a plurality of areas along the flow direction of the gas in the plurality of nozzles 249a, 249b, 249c. In the above process (a) and the above process (b), the plurality of areas are divided into There are different ways to control the temperature of the area, so it is better to change the temperature. For example, the reaction tube 203 shown in FIG. 1 is divided into a plurality of areas in the vertical direction, and the control unit (controller 121) is preferably capable of controlling the temperature of the heater 207 for each of the plurality of areas.

For example, in the cleaning process of the above process (a), it is preferable to perform temperature control by setting a temperature gradient so that the temperature of the upper region is higher than the temperature of the lower region. By setting such a temperature gradient, even if the amount of purge gas reaching the upper side of the nozzle or the upper side of the reaction tube is reduced, by increasing the temperature on the upper side, the reactivity of the purge gas can be increased, and the purge gas can be discharged from the nozzle. Or clean the reaction tube evenly from the upper side to the lower side. In addition, when providing a process for supplying additional gas after the above-mentioned process (a), it is preferable to provide temperature control with the same temperature gradient.

Furthermore, in the fluorine deactivation treatment in the above-mentioned step (b), it can be controlled so that all regions have substantially the same temperature. This makes it possible to perform fluorine deactivation processing in the nozzles 249a, 249b, and 249c corresponding to all areas. In addition, the substantially uniform temperature referred to here means, for example, that the temperature difference between the highest temperature area and the lowest temperature area is within 3°C.

On the other hand, as shown in FIG. 1 , when the gas flow direction in the nozzles 249a, 249b, and 249c is from bottom to top, in the fluorine deactivation treatment in the above step (b), the lower end side area is It is better to control the temperature to be higher than the temperature in other areas. Accordingly, the hydrogen-oxygen-containing gas is preliminarily heated in the lower end region, in other words, in the upstream region, thereby shortening the heating time to reach the optimal reaction temperature in the reaction tube 203 .

In addition, the first reaction is controlled by the second heater 207a provided downstream of the valve body 243d of the gas supply pipe 232d that supplies the first reaction gas and the valve body 243e of the gas supply pipe 232e that supplies the second reaction gas. The gas and the second reaction gas are preliminarily heated, and residual fluorine in the gas supply pipe 232a up to the nozzle 249a can be removed. Similarly, the first reaction is controlled by the second heater 207b provided downstream of the valve body 243b of the gas supply pipe 232b that supplies the first reaction gas and the valve body 243h of the gas supply pipe 232h that supplies the second reaction gas. The gas and the second reaction gas are preliminarily heated, and residual fluorine in the gas supply pipe 232b up to the nozzle 249b can be removed. Furthermore, the first reaction is controlled by the second heater 207c provided downstream of the valve body 243k of the gas supply pipe 232k that supplies the first reaction gas and the valve body 243c of the gas supply pipe 232c that supplies the second reaction gas. The gas and the second reaction gas are preliminarily heated, and residual fluorine in the gas supply pipe 232c up to the nozzle 249c can be removed. In addition, here, although an example is shown in which the first reaction gas and the second reaction gas are heated in different gas supply pipes, the first reaction gas and the second reaction gas may be mixed and then heated.

According to the cleaning method of the semiconductor device caused by the above-mentioned processes (a) and (b), the cleaning process and the fluorine deactivation process in the reaction tube 203 and the nozzles 249a, 249b, and 249c can be performed using the cleaning gas.

(2-4) Second substrate (wafer 200) processing When the cleaning process and fluorine deactivation process in the reaction tube 203 and the nozzles 249a, 249b, 249c are completed through the above-mentioned processes (a) and (b), the next substrate (wafer 20 ) is carried into the reaction tube 203 described above. The processing of the substrate (wafer 200) described in the above (2-1) is performed on the next substrate (wafer 200) that is loaded. [Example]

Hereinafter, an embodiment of the method for manufacturing the semiconductor device of the present invention will be described.

In addition, the description of a numerical range such as "75 to 200°C" in the following description means that the range includes the lower limit and the upper limit. Accordingly, for example, "75~200℃" means "above 75℃ and below 200℃". The same is true even for other numerical ranges.

＜Experiment Summary＞ In the Examples and Comparative Examples, first, after the film forming process of forming a film on the wafer was performed several times, the cleaning process and the gas adding process of the above process (a) were alternately repeated a plurality of times. Furthermore, after performing the fluorine deactivation treatment in the above step (b), the film forming treatment is repeated again. The film thickness was measured for the wafers obtained in each film formation process.

＜Film formation treatment＞ The following film formation process mentioned in (2-1) above is performed. In addition, steps such as installation and initial cleaning before the film formation process are omitted.

(raw material gas → P/V → first reaction gas + second reaction gas → P/V)×n

First, after the wafer 200 is loaded into the reaction tube 203, as step 1, HCDS gas as a source gas is supplied into the reaction tube 203 from the gas supply pipe 232a (first pipe) and the nozzle 249a (first nozzle).

Next, as step 2, while supplying N ₂ gas as a purge gas (or not supplying it) from the gas supply pipe 232n through the first pipe and the first nozzle, the inside of the reaction tube 203 is evacuated to eliminate residual process gas. Indoor raw gas.

Furthermore, as step 3, H ₂ gas as the first reaction gas is supplied to the wafer 200 in the reaction tube 203 via the gas supply pipe 232b (second pipe) and the nozzle 249b (second nozzle), while passing the gas The supply pipe 232c (third pipe) and the nozzle 249c (third nozzle) supply O ₂ gas as the second reaction gas.

Finally, as step 4, while supplying the purge gas from the gas supply pipe 232o through the second pipe and the second nozzle, and simultaneously supplying the purge gas from the gas supply pipe 232p through the third pipe and the third nozzle, the inside of the reaction tube 203 is Vacuum exhaust is performed to remove the first reaction gas and the second reaction gas remaining in the processing chamber.

Repeat steps 1 to 4 above a specific number of times. In addition, the processing conditions in each step are as follows. Raw gas supply flow rate: 0.01~2slm, preferably 0.1~1slm Purification gas supply flow: 0~10slm The first reaction gas supply flow rate: 0.1~10slm Second reaction gas supply flow rate: 0.1~10slm Each gas supply time: 1~120 seconds, preferably 1~60 seconds Processing temperature: 250~800℃, preferably 400~700℃ Processing pressure: 1~2666Pa, preferably 67~1333Pa

＜Cleaning treatment＞ After unloading the wafer after the film formation process, the cleaning process mentioned in (2-2) above is performed using all the first nozzle, the second nozzle, and the third nozzle. Here, the following processing is performed on each nozzle. Each process is performed in parallel. 1st nozzle (nozzle 249a): Process C 2nd nozzle (nozzle 249b): Process A 3rd nozzle (nozzle 249c): Process B

That is, during the cleaning process, the N ₂ gas as the inert gas is continuously supplied from the gas supply pipe 232n through the first pipe and the first nozzle. Furthermore, F ₂ gas as the cleaning gas and NO as the additive gas are sequentially supplied from the gas supply pipe 232i and the gas supply pipe 232j via the second pipe and the second nozzle in a manner corresponding to the order of process A. gas. Furthermore, the cleaning gas and the additive gas are sequentially supplied through the gas supply pipe 2321 and the gas supply pipe 232m through the third pipe and the third nozzle in a manner corresponding to the order of process B. Here, process A and process B are executed simultaneously using their respective nozzles.

The above-mentioned supply of cleaning gas and supply of additional gas are repeated a specific number of times. In addition, the processing conditions are as follows. Cleaning gas supply flow: 1~20slm, preferably 5~15slm. Added gas supply flow: 0.1~2slm, preferably 0.5~1.5slm Each gas supply time: 10~120 seconds, preferably 20~40 seconds Processing temperature: 250~400℃, preferably 250~350℃ Processing pressure: 1~1000Torr, preferably 10~500Torr

＜Fluorine deactivation treatment＞ After the above-mentioned cleaning process, the fluorine deactivation process mentioned in the above (2-3) is performed using all the first nozzle, the second nozzle, and the third nozzle.

First, H ₂ gas as the first reaction gas from the gas supply pipe 232 d and O ₂ gas as the second reaction gas from the gas supply pipe 232 e are supplied into the reaction tube 203 through the first pipe and the first nozzle. supply. At the same time, the first reaction gas is supplied from the gas supply pipe 232b and the second reaction gas is supplied from the gas supply pipe 232h into the reaction tube 203 through the second pipe and the second nozzle. At the same time, the first reaction gas is supplied from the gas supply pipe 232k and the second reaction gas is supplied from the gas supply pipe 232c into the reaction tube 203 via the first pipe and the first nozzle. The ratio of the supply flow rates of the first reaction gas and the second reaction gas is approximately 1:1. Other processing conditions are as follows. The first reaction gas supply flow rate: 1~10slm The second reaction gas supply flow rate: 1~10slm Each gas supply time: 30~300 minutes, 100~150 minutes is optimal. Processing temperature: 600~800℃, processing pressure: 5~ 133Pa, preferably 5~30Pa

In addition, in the comparative example, the first reaction gas and the second reaction gas are not supplied from the first pipe and the first nozzle, and only the first reaction gas from the gas supply pipe 232b is supplied from the second pipe and the second nozzle. The second reaction gas from the gas supply pipe 232c is supplied from the third pipe and the third nozzle.

＜Result＞ The results of film formation stability in Comparative Examples and Examples are shown in Figures 4 and 5 respectively. In addition, in FIGS. 4 and 5 , the vertical axis of the graph represents the film thickness of the wafer 200 (the increase or decrease relative to the reference film is expressed in Angstrom units), and the horizontal axis represents the number of film forming processes. In addition, the dotted line in both figures represents the reference film thickness. In addition, in both figures, arrows indicate the timing of performing the cleaning process and the fluorine deactivation process.

In the comparative example, after the third film formation process, the cleaning process and the fluorine deactivation process were performed, and the film thickness immediately decreased by about 0.5 from the standard film thickness. In particular, the reduction in film thickness is more significant after the 41st treatment.

On the other hand, in the Example, after the sixth film-forming process, the cleaning process and the fluorine deactivation process were performed. Although the film thickness immediately decreased, the amount of decrease did not reach 0.1. Moreover, after the number of treatments reached 14, the film thickness became stable.

In the comparative example, as shown in the schematic diagram of FIG. 6 , the first reaction gas is supplied only from the nozzle 249b (second nozzle), and the second reaction gas is supplied only from the nozzle 249c (third nozzle), and not from the nozzle 249a. (The first nozzle) supplies the first reaction gas and the second reaction gas. As a result, in the area indicated by B in the figure including the processing chamber 201 and the exhaust pipe 231 in the reaction tube 203, the first reaction gas and the second reaction gas cannot be mixed sufficiently, so the fluorine deactivation is fully performed. handle. However, it is estimated that in the vicinity of the nozzles 249a, 249b, and 249c indicated by A in the figure, the first reaction gas and the second reaction gas are not sufficiently mixed, so that the fluorine deactivation treatment cannot be fully performed, and the subsequent formation is Membrane treatment has a negative impact.

On the other hand, in the embodiment, as shown in the schematic diagram of FIG. 7 , the first reaction gas and the first reaction gas are supplied from all of the nozzle 249a (first nozzle), nozzle 249b (second nozzle), and nozzle 249c (third nozzle). Both sides of the second reaction gas. As a result, it is inferred that the first reactive gas and the second reactive gas can be fully mixed not only in the B area but also in the A area in the figure, so the fluorine deactivation treatment can be fully performed and the subsequent film formation can be performed satisfactorily. handle.

＜Other aspects of this disclosure＞ The aspect of this disclosure has been concretely described above. However, the aspect of this disclosure is not limited to the above-mentioned aspect, and various changes can be made within the scope which does not deviate from the gist.

In the film formation process, a film may be formed on the wafer 200 by the gas supply sequence shown below. The above-described cleaning process can be appropriately applied even to nozzles or reaction tubes formed of the materials shown below.

(Si-containing raw material gas→carbon-containing gas→nitriding gas→oxidizing gas (second reaction gas))×n⇒SiOCN (Si-containing raw material gas→oxidizing gas (second reaction gas)→nitriding gas)×n⇒SiON (Si-containing raw material gas→nitriding gas→oxidizing gas (second reaction gas))×n⇒SiON (Si-containing raw material gas→nitriding gas)×n⇒SiN Here, a carbon-containing gas system such as propylene gas (C ₃ H ₆ gas), nitrogen gas system such as ammonia gas (NH ₃ gas).

The recipes used in each process are prepared individually according to the content of the process, and are preferably stored in the memory device 121c via telecommunications lines or the external memory device 123. Moreover, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the content of the process from among the plurality of recipes stored in the memory device 121c. According to this, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using one substrate processing apparatus. Furthermore, the burden on the operator can be reduced, and various processes can be started quickly while avoiding operation errors.

The above-mentioned recipe is not limited to a newly created one, and may be prepared by changing an existing recipe already installed in the substrate processing apparatus, for example. When the recipe is changed, the changed recipe may be installed in the substrate processing apparatus via a telecommunications line or a recording medium that records the recipe. Furthermore, even if the input/output device 122 of the existing substrate processing apparatus is operated, the existing recipe installed in the substrate processing apparatus may be directly changed.

In the above-mentioned aspect, the cleaning gas is explained using F ₂ gas or NF ₃ gas as an example of the fluorine-containing gas. The present disclosure is not limited to the above aspect, and examples thereof include gases such as hydrogen fluoride (HF) gas, carbon tetrafluoride (CF ₄ ), and chlorine trifluoride (ClF ₃ ). In addition, it is preferable that the cleaning gas contains at least one of F ₂ , NF ₃ , HF, CF ₄ and ClF ₃ .

In the above aspect, an example in which fluorine-containing gas is used as the cleaning gas for cleaning will be described. The present disclosure is not limited to the above aspect, and is applicable even when a cleaning gas containing a halogen element is used, for example. Here, the halogen element is chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc.

In the above aspect, an example in which a film is formed using a batch-type substrate processing apparatus that processes a plurality of substrates at a time will be described. The present disclosure is not limited to the above aspect. For example, the present disclosure may be suitably applied even when a film is formed using a piece-by-piece substrate processing apparatus that processes one or several substrates at a time. Furthermore, in the above aspect, an example in which a film is formed using a substrate processing apparatus of a hot wall type processing furnace will be described. The present disclosure is not limited to the above aspect, and can be appropriately applied even when a film is formed using a substrate processing apparatus having a cold wall type processing furnace.

Even when these substrate processing apparatuses are used, each process can be performed with the same processing procedures and processing conditions as the above-mentioned aspects, and the same effects as the above-mentioned aspects can be obtained.

Furthermore, the above aspects can be used in appropriate combinations. The processing program and processing conditions at this time can be, for example, the same as those in the above aspect.

121:Control Department 200: Wafer (substrate) 201:Processing room 203:Reaction tube 232a: Gas supply pipe (first pipe) 232b: Gas supply pipe (second pipe) 232c: Gas supply pipe (3rd pipe) 249a: Nozzle (1st nozzle) 249b: Nozzle (2nd nozzle) 249c: Nozzle (3rd nozzle)

[Fig. 1] is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in one aspect of the present disclosure, and is a diagram showing a portion of the processing furnace in a longitudinal sectional view. [Fig. 2] is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus suitable for use in one aspect of the present disclosure, and is a cross-sectional view along line A-A in Fig. 1 showing a part of the processing furnace. 3 is a schematic structural diagram of a controller of a substrate processing apparatus suitable for use in one aspect of the present disclosure, and a diagram showing a control system of the controller in a block diagram. [Fig. 4] is a graph showing the results of film formation stability in comparative examples. [Fig. 5] is a graph showing the results of film formation stability in Examples. [Fig. 6] is a schematic diagram showing deactivation of residual fluorine in a comparative example. [Fig. 7] is a schematic diagram showing deactivation of residual fluorine in Example.

115: Crystal boat lifter

115s: Damper switch mechanism

121:Control Department

200: Wafer (substrate)

201:Processing room

202: Treatment furnace

203:Reaction tube

207:Heater

207a: 2nd heater

207b: 2nd heater

207c: 2nd heater

209:Biver pipe

217:Jingzhou

218:Heat insulation board

219:Sealing cover

219s:Baffle

220a:O-ring

220b:O-ring

220c:O-ring

231:Exhaust pipe

231a:Exhaust port

232a~232p: Gas supply pipe

241a~241p:MFC

243a~243p: valve body

244:APC valve

245: Pressure sensor

246: Vacuum valve

248:Integrated supply system

255:Rotation axis

263:Temperature sensor

267: Rotating mechanism

249a: Nozzle (1st nozzle)

249b: Nozzle (2nd nozzle)

249c: Nozzle (3rd nozzle)

249d:Main area

250a:Gas supply hole

250b:Gas supply hole

250c: Gas supply hole

Claims (20)

A method for cleaning a nozzle, which includes: (a) supplying a fluorine-containing cleaning gas to at least one of the plurality of nozzles after a substrate is processed and removed from a reaction tube having a plurality of nozzles: (d) ) among the above-mentioned plurality of nozzles, the process of supplying nitrogen- and oxygen-containing gas to at least one of the above-mentioned nozzles after performing the process of (a); and (b) after performing the process of (d), performing the process of above-mentioned (a) After the process, the at least one nozzle is supplied with a gas containing hydrogen and oxygen. The nozzle cleaning method of claim 1, wherein in the process of (a), the cleaning gas is not supplied to nozzles other than the at least one nozzle among the plurality of nozzles. The nozzle cleaning method of claim 1, wherein in the process of (a), the supply amount of gas to nozzles other than at least one nozzle among the plurality of nozzles is substantially zero. A method for cleaning nozzles as claimed in claim 1, wherein the above process (a) is performed on all of the plurality of nozzles. The nozzle cleaning method of claim 1, wherein the above process (a) is performed on all the plurality of nozzles at the same time. The method for cleaning a nozzle according to any one of claims 1 to 5, wherein the above-mentioned cleaning gas system includes at least one of F ₂ gas and NF ₃ gas. The nozzle cleaning method of claim 1 further includes (e) the process of alternately performing the above-mentioned process (a) and the above-mentioned process (d). The nozzle cleaning method of claim 1, wherein (f) in the above-mentioned process (b), the plurality of nozzles are heated by a heater in a manner that the gas containing hydrogen and oxygen is activated in the nozzles. A method for cleaning a nozzle according to claim 8, wherein in the step (f), the main areas of the plurality of nozzles are heated to a substantially uniform temperature. The method for cleaning a nozzle according to claim 8, wherein in the step (f), the heating is performed by the heater disposed in the reaction tube at a position corresponding to the area where the substrate is located. A method for cleaning a nozzle according to claim 10, wherein the substrate is a product substrate. The method of cleaning a nozzle according to claim 8, wherein one or both of the plurality of nozzles and the heater are arranged so that at least an area provided with holes in the plurality of nozzles is in a position facing the heater. The nozzle cleaning method of claim 8, wherein the heater is divided into a plurality of regions along the flow direction of the gas in the plurality of nozzles, (g) in the above process (a) and the above process ((g) In b), the temperature is changed in such a way that the temperature control of the plurality of areas mentioned above is different. For example, the method for cleaning the nozzle of claim 13, wherein In the above step (b), the temperature of at least a region corresponding to the processing region of the substrate among the plurality of regions is controlled to be substantially the same temperature. A method for cleaning a nozzle according to claim 13, wherein in the step (b), the temperature of the lower end region among the plurality of regions is controlled to be higher than the temperature of other regions. The method for cleaning a nozzle according to claim 1, further comprising: (h) heating the gas containing hydrogen and oxygen with a second heater outside the reaction tube. A substrate processing method, which includes: (a) supplying a fluorine-containing cleaning gas to at least one of the plurality of nozzles after the substrate is processed and moved out of a reaction tube having a plurality of nozzles; (d) Among the above-mentioned plurality of nozzles, at least one of the above-mentioned nozzles supplies the gas containing nitrogen and oxygen after the process of the above-mentioned (a) is carried out; (b) after the process of the above-mentioned (d), the process of the above-mentioned (a) is carried out (c) After the process in (b) above, the process of loading the next substrate into the reaction tube. A method of manufacturing a semiconductor device, which includes: (a) supplying a fluorine-containing cleaning gas to at least one of the plurality of nozzles after a substrate is processed in a reaction tube having a plurality of nozzles, and (d) ) For the plurality of nozzles mentioned above, after performing the process (a) above, The process of supplying gas containing nitrogen and oxygen to at least one nozzle; (b) after the process of the above (d), supplying the gas containing hydrogen and oxygen to the at least one nozzle after the process of the above (a). The process; and (c) after the process in (b) above, the process of moving the next substrate into the above-mentioned reaction tube. A substrate processing apparatus includes: a reaction tube for processing a substrate inside; a transport mechanism for loading and unloading substrates into the reaction tube; a plurality of nozzles for supplying various gases to the reaction tube; and a cleaning gas supply system , which supplies cleaning gas to at least one nozzle among the plurality of nozzles; a hydrogen-and-oxygen-containing gas supply system, which supplies gas containing hydrogen and oxygen to at least one of the above-mentioned nozzles; and a control unit, which is configured as After the substrate is processed in a reaction tube having a plurality of nozzles and is unloaded, it is possible to perform: (a) a process of supplying a fluorine-containing cleaning gas to at least one of the plurality of nozzles; (d) a process of supplying a fluorine-containing cleaning gas to any of the plurality of nozzles. , after the above-mentioned (a) process is carried out, the above-mentioned at least one nozzle is supplied with gas containing nitrogen and oxygen; (b) after the above-mentioned (d) process, the above-mentioned at least one nozzle after the above-mentioned (a) process is carried out The nozzle supplies a gas containing hydrogen and oxygen; and (c) after the process in (b) above, the method of loading the next substrate into the reaction tube, Control the above-mentioned conveying mechanism, the above-mentioned cleaning gas supply system, and the above-mentioned hydrogen-oxygen-containing gas supply system. A program recorded on a computer-readable recording medium, in which, after a substrate is processed in a reaction tube having a plurality of nozzles and moved out, the computer causes the substrate processing device to execute: (a) at least one of the plurality of nozzles The step of supplying fluorine-containing cleaning gas to the nozzles; (d) the step of supplying nitrogen- and oxygen-containing gas to at least one of the plurality of nozzles after performing the process of (a) above; (b) in the above-mentioned step After the process of (d), the step of supplying gas containing hydrogen and oxygen to the above-mentioned at least one nozzle after the process of the above-mentioned (a); and (c) After the process of the above-mentioned (b), the step of supplying gas containing hydrogen and oxygen to the above-mentioned reaction tube Processing steps for moving in the next substrate.

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